KR20180103914A - Vulcanizable compositions based on hydrogenated nitrile rubbers, process for their preparation and uses thereof - Google Patents

Abstract

The present invention is based on a hydrogenated nitrile rubber and has a specific surface area (N ₂ surface area) of less than 10 m ² / g, including 40 wt% or more of silicate (SiO ₂ ) and 10 wt% or more of aluminum oxide (Al ₂ O ₃ ) Inorganic fillers, basic sodium silicates and donor based crosslinking systems. The present invention also relates to the preparation of such vulcanizable compositions, and also to the vulcanized products produced therefrom, and in particular to their use in seals, belts, roll coatings, tubes and cables.

Description

Vulcanizable compositions based on hydrogenated nitrile rubbers, process for their preparation and uses thereof

The present invention relates to an inorganic filler having a specific surface area (N ₂ surface area) of less than 10 m ² / g, comprising hydrogenated nitrile rubber, at least 40% by weight of silicate (SiO ₂ ) and at least 10% by weight of aluminum oxide (Al ₂ O ₃ ) It relates to a vulcanizable composition containing a cross-linking system based on a radical donor-basic sodium silicate and freedom. The present invention also relates to the preparation of these vulcanizable compositions, and also to the vulcanizates prepared therefrom and their use, in particular in gaskets , belts, roll coatings, hoses and cables.

Hydrogenated nitrile rubbers are required in gaskets which exhibit high resistance to high and low temperatures and at the same time high oil resistance. Resistant nitrile rubbers, in particular , hydrogenated nitrile rubbers which meet many requirements of the EN 549 standard and which have low low temperature compression set values as well as low temperature high compression set values and strong high temperature aging resistance at 175 ° C, in particular hardness stability and breaking elongation stability Rubber is particularly required.

The properties of the vulcanizate depend on the interaction of the constituents of the vulcanizable composition. The hydrogenated nitrile rubber as the main constituent as well as the filler used in particular are also decisive factors. There are many known inorganic and synthetic fillers having reinforced and non-reinforced properties.

Those skilled in the art understand that the term " reinforced " is meant to refer to all of the rubber-filler interactions that are evident in the physical properties, not only in the comparative bond state but also in the cross-linked state.

The reinforced (active) filler changes the viscoelastic properties through interaction with the rubber matrix. They increase the viscosity of the rubber and improve the fracture behavior of the vulcanizate, such as breaking elongation, resistance to abrasion and abrasion.

Examples of reinforcing fillers include certain carbon blacks , precipitated silicas with high specific surface area and fumed silicas with high specific surface area. However, the most frequently used filler is carbon black.

The non-reinforced (inert) filler dilutes the rubber matrix. This has the effect of impairing certain properties, such as the breakdown energy (i.e., the integration of the stress-strain curve); (F. Roethemeyer, F. Sommer, " Kautschuktechnologie: Werkstoffe-Verarbeitung-Produkte " [Rubber technology: materials-processing-products] 2013, 3rd Edition , pp. 261-262). It is known from the literature that non-reinforcing fillers can improve compression set.

The filler in the form of a 5 wt% solution in water has a characteristic pH. This pH can be used to elicit the distinction between acidic and basic fillers .

EP-A-0 795 580 discloses the use of hydrogenated nitrile rubbers (HNBR), inorganic fillers (calcium carbonate), additional inorganic fillers (Carplex 1120, wet silica) in Tables 1 and 2 on pages 8 and 9, (Examples 1 to 7 and Comparative Examples 2 and 3) comprising a metal oxide (ZnO) and a peroxide compound (Peroxymon F-40) derived from a Group 2 element of the periodic table . In the embodiment of Table 1, for example, HNBR, basic sodium silicate, at least 40% by weight of silicate (SiO _2), and 10% or more of aluminum oxide by weight (Al ₂ O ₃₎ a specific surface area including the (N ₂ surface area) is 10 m ² / lt; RTI ID = 0.0 > g / g < / RTI >

In DE102008060258 is a specific surface area of 1.5 m ² / g comprising a nitrile rubber (HNBR), 90.0% by weight of SiO ₂ and Al ₂ O ₃ of 4.0% by weight of hydrogenated at paragraph [0057] on page 7, the inorganic filler (key Ezer Discloses a rubber composition (Example I) comprising Kieselgur Celite 281, an active filler (Vulcasil) and a peroxide compound (Perkadox 14/40). The inorganic filler comprises less than 10% Al ₂ O ₃ . The definition of " vulcanization " is not disclosed.

WO-A-2004/035669 discloses a hydrogenated nitrile rubber (HNBR), inorganic filler (Satintone SP-33 Kaolin Clay), silicate (SiO ₂ ) 233) and peroxide compounds (Vulcup 40KE). Compositions with basic sodium silicate are not disclosed.

The use of basic sodium silicates is principally known. The basic silicate has a pH (in water of 5% by weight) in excess of 7, measured according to DIN ISO 787/9. Examples of a basic sodium silicate is a sodium aluminum silicate (such as fire kasil (Vulkasil) ^® A1, the fifth Rex ^{(Zeolex) ® 23, HM500)} .

WO2011 / 023771 discloses a hydrogenated nitrile rubber (HNBR) inorganic filler ( celite , specific surface area 1.5 m ² / g; 90.0 wt% SiO ₂ and 4.0 wt% Al ₂ O ₃ ), silicate Cousil VP 6508 (surface-modified precipitated silica with an organosilane coating); and a peroxide compound (1,3-bis- (tert-butylperoxy-iso Propyl) -benzoyl, percadox 14-40; percadox 14s).

EP-A-0 778 327 discloses the use of butadiene-acrylonitrile-acrylate copolymers in vulcanizable compositions, organic peroxides as crosslinking agents, metal oxides as vulcanization aids and basic sodium silicates as reinforcing fillers. However, the literature discloses that the specific surface area (N ₂ surface area) of the hydrogenated nitrile rubber, basic sodium silicate, peroxide compound and at least 40 wt% silicate (SiO ₂ ) and at least 10 wt% aluminum oxide (Al ₂ O ₃ ) There is no disclosure of a vulcanizable composition comprising an inorganic filler having a specific surface area of less than 10 m < ² > / g.

WO-A-2010/030860 discloses the use of hydrogenated nitrile rubber (HNBR), inorganic fillers (MgO, Maglit; ZnO, Kadox), basic sodium silicate (Zeolex 23) 14 < / RTI > pages). More than 40% by weight of silicate (SiO _2), and 10% or more of aluminum oxide by weight (Al ₂ O ₃₎ a specific surface area (N ₂ surface area), including a composition comprising an inorganic filler is less than 10 m ² / g is not disclosed .

Prior art document is more than 40% by weight of silicate (SiO ₂₎ and 10, a specific surface area including the% by weight or more of aluminum oxide _{(Al 2 O 3) (N} 2 surface area) is 10 m in ² / g less than the inorganic filler and a basic sodium silicate Does not disclose vulcanizable compositions of hydrogenated nitrile rubbers having combinations.

The vulcanizates disclosed in the prior art do not provide satisfactory values with respect to high temperature compression set and aging resistance, especially with respect to hardness stability and breaking elongation stability.

It is an object of the present invention to provide vulcanizable compositions and vulcanizates thereof based on hydrogenated nitrile rubbers, wherein the vulcanizates have the following.

1. High temperature compression set values (CS) of less than 45% , preferably less than 40% after storage at 175 DEG C for 168 hours .

2. Hardness change (DELTA H) of 10% or less, preferably 8% or less after storage at 175 DEG C for 168 hours, and

3. After storage at 175 ° C for 168 hours, a change in elongation at break (ΔEB) of less than 35% , preferably less than 30%

Surprisingly, based on the total amount of the inorganic filler of more than 40% by weight of silicate (SiO _2), and 10% or more of aluminum oxide by weight (Al ₂ O ₃₎ a specific surface area (N ₂ surface area) is 10 m ² / g is less than the inorganic filler containing the , for example, Paul reseuta (Polestar) ^® 200R, and a basic sodium silicate, for example, fire the combination of the hydrogenated nitrile rubber in kasil ^® A1 is a peroxy after draw crosslinked, comply with the required characteristics, and therefore lower hot compression It has now been found that it leads to vulcanizates having excellent aging resistance as well as permanent deformation values .

Accordingly, the present invention

(a) at least one hydrogenated nitrile rubber ,

(N ₂ surface area) comprising at least 40% by weight of silicate (SiO ₂ ) and at least 10% by weight of aluminum oxide (Al ₂ O ₃ ) based on the total amount of component (b) is 10 m ² / g At least one inorganic filler

(c) at least one basic sodium silicate and

(d) at least one peroxide compound

≪ / RTI >

This characteristic profile comprises a hydrogenated nitrile rubber but does not comprise any combination of the two components (b) and (c) but instead comprises a conventional known vulcanization (C) comprising only one of each of components b) and c) It can not be achieved by using a casting composition.

A preferred vulcanizable composition comprises

(a) 100 parts by weight of at least one hydrogenated nitrile rubber,

(N ₂ surface area) comprising at least 40% by weight of silicate (SiO ₂ ) and at least 10% by weight of aluminum oxide (Al ₂ O ₃ ) based on the total amount of component (b) is 10 m ² / g 50 to 100 parts by weight, preferably 60 to 90 parts by weight, of at least one inorganic filler,

(c) 5 to 50 parts by weight, preferably 10 to 30 parts by weight, of at least one basic sodium silicate with a pH in water (5% by weight in water) of more than 7, measured according to DIN ISO 787/9, and

(d) 1 to 20 parts by weight, preferably 2 to 10 parts by weight, of at least one peroxide compound

Lt; / RTI >

(a) 100 parts by weight of at least one hydrogenated nitrile rubber ,

(b) 50 to 60 wt.%, preferably 55 wt.% SiO ₂ and 35 to 45 wt.%, preferably 41 wt.% Al ₂ O ₃ , based on the total amount of component (b) 50-100 parts by weight of calcined kaolin having a pH (water 5% by weight in water) of 6.5 ± 0.5 and a (BET) surface area of 8.5 m ² / g measured according to ISO 9277, measured according to ISO 787/9, Preferably 60 to 90 parts by weight,

(c) the pH (5% by weight in water) in water measured according to DIN ISO 787/9 is 11.3 ± 0.7, the content of volatile constituents measured according to DIN ISO 787/2 is 5.5 ± 1.5, and ISO 9277 5 to 50 parts by weight, preferably 10 to 30 parts by weight, of sodium aluminum silicate having a (BET) surface area of 65 占 15,

(d) at least one peroxide compound , preferably at least one peroxides selected from the group consisting of dicumyl peroxide, tert-butyl cumyl peroxide, bis (tert-butylperoxyisopropyl) benzene, 2,5-dihydroperoxide, 2,5-dimethylhex-3-in 2,5-dihydroperoxide or dibenzoyl peroxide in an amount of 1 to 20 parts by weight, preferably 2 to 10 parts by weight

≪ / RTI > is particularly preferred.

Another characteristic of the vulcanizable composition of the present invention is that the vulcanized product

· High temperature compression set values of less than 45% measured in accordance with DIN ISO 850 Part A after 168 hours of storage at 175 ° C,

· Hardness changes of less than 10% measured according to DIN 53508 after 168 h at 175 ° C and

· A breaking elongation change of less than 35% measured according to DIN 53508 after 168 h at 175 ° C

.

The vulcanizable composition of the present invention comprises at least one hydrogenated nitrile rubber as component (a) .

Hydrogenated nitrile rubber:

For the purposes of the present application, hydrogenated nitrile rubbers (HNBR) are copolymers and / or copolymers based on one or more conjugated dienes and one or more alpha, beta -unsaturated nitrile monomers and also optionally other copolymerizable monomers Wherein the copolymerized diene units are hydrogenated in whole or in part.

For purposes of the present application, "hydrogenated" or "hydrogenated" means at least 50%, preferably at least 85%, particularly preferably at least 95% of the double bonds originally present in the nitrile rubber.

Any known α, β- unsaturated nitriles are α, β-, and can be used as the unsaturated nitrile, acrylonitrile, methacrylonitrile, acrylonitrile, ethacrylic, or mixtures thereof, such as (C ₃ -C ₅₎ -α, beta -unsaturated nitrile is preferred. Acrylonitrile is particularly preferred.

The conjugated dienes can be of any type. (C ₄ -C ₆ ) conjugated diene is preferred. 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene or mixtures thereof are particularly preferred. Particularly preferred are 1,3-butadiene and isoprene or mixtures thereof. 1,3-butadiene is very particularly preferred.

The proportions of conjugated dienes and alpha, beta -unsaturated nitriles in the hydrogenated nitrile rubbers can vary widely. The proportion of the conjugated diene or the whole is usually in the range of 40 to 90% by weight, preferably in the range of 50 to 80% by weight, based on the whole polymer. The proportion of the .alpha.,. beta.-unsaturated nitrile or the whole is usually in the range of 10 to 60% by weight, preferably 20 to 50% by weight based on the whole polymer. The amount that can be used for the additional monomer ranges from 0.1 to 40% by weight, preferably from 1 to 30% by weight, based on the total polymer. In this case, the corresponding proportion of the conjugated diene (s) and / or?,? - unsaturated nitrile (s) is replaced by a proportion of additional monomers, wherein the ratio of all monomers in each case is 100 wt.

The preparation of these hydrogenated nitrile rubbers suitable for the vulcanizable compositions of the present invention is well known to those skilled in the art.

(See, for example, Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry] Vol. 14/1, Georg Thieme Verlag Stuttgart 1961) provides a comprehensive description of the initial preparation of nitrile rubbers by polymerization of the above monomers .

Subsequent hydrogenation of the nitrile rubber described above for a given hydrogenated nitrile rubber can occur in a manner known to those skilled in the art.

In principle, the hydrogenation of the nitrile rubber can be carried out using a homogeneous or heterogeneous hydrogenation catalyst.

As described in WO-A-01/77185, which for example, homogeneous catalysts, such as hydrogen in combination with a catalyst or other catalyst known as a "catalyst ((PPh _{3) 3} RhCl) in Wilkinson (Wilkinson) It is common to use rhodium or titanium as the catalyst, but it is also possible to use platinum, iridium, palladium, rhenium, ruthenium, osmium, cobalt or copper in the form of metal A-25 39 132, EP-A-134 023, DE-OS-35 41 689, DE- OS-35 40 918, EP-A-298 386, DE-OS-35 29 252, DE-OS-34 33 392, US-A-4,464,515 and US-A-4,503,196).

Suitable catalysts and solvents for homogeneous-phase hydrogenation are described below and are also known from DE-A-25 39 132 and EP-A-0 471 250.

Selective hydrogenation can be accomplished, for example, in the presence of a rhodium-containing catalyst. For example, a catalyst of the following formula can be used.

(R ¹ _m B) _l RhX _n

here

R ¹ is the same or different and is a C ₁ -C ₈ alkyl group, a C ₄ -C ₈ cycloalkyl group, a C ₆ -C ₁₅ aryl group or a C ₇ -C ₁₅ aralkyl group,

B Is phosphorus, arsenic, sulfur or a sulfoxide group S = O,

X Is hydrogen or an anion, preferably a halogen, particularly preferably chlorine or bromine,

l Is 2, 3 or 4,

m Is 2 or 3, and

n Is 1, 2 or 3, preferably 1 or 3.

Preferred catalysts are tris (triphenylphosphine) rhodium (I) chloride, tris (triphenylphosphine) rhodium (III) chloride and tris (dimethyl sulphoxide) rhodium (III) chloride, and the formula ((C ₆ H _{5) 3} P) ₄ RhH tetrakis- (triphenylphosphine) rhodium hydride and triphenylphosphine are all or partly substituted by tricyclohexylphosphine. Small amounts of catalyst may be used. A suitable amount is in the range of 0.01 to 1% by weight, preferably 0.03 to 0.5% by weight, particularly preferably 0.1 to 0.3% by weight, based on the weight of the polymer.

It is generally preferred to use the catalyst with a co-catalyst which is a ligand of the formula R ¹ _m B, wherein R ¹ , m and B have the meanings as defined above for the catalyst. Preferably, m is 3, B is phosphorus, and the moieties R < ¹ > may be the same or different. Wherein the co-catalyst is selected from the group consisting of trialkyl, tricycloalkyl, triaryl, triaralkyl, diarylmonoalkyl, diarylmonocycloalkyl, dialkylmonoaryl, dialkyl-monocycloalkyl, dicycloalkylmonoaryl, It is preferred to have an alkyl monoaryl moiety.

Examples of co-catalysts are found as examples in US-A-4,631,315. A preferred co-catalyst is triphenylphosphine. The amount of the co-catalyst to be used is preferably in the range of 0.3 to 5 wt.%, Particularly preferably in the range of 0.5 to 4 wt.%, Based on the weight of the nitrile rubber to be hydrogenated. In addition, the weight ratio of rhodium-containing catalyst to co-catalyst is preferably in the range of 1: 3 to 1:55, particularly preferably in the range of 1: 5 to 1:45. The amount of the co-catalyst based on 100 parts by weight of the nitrile rubber to be hydrogenated is suitably 0.1 to 33 parts by weight, preferably 0.5 to 20 parts by weight, very particularly preferably 1 to 5 parts by weight, Is greater than 2 parts by weight but less than 5 parts by weight based on 100 parts by weight.

The actual performance of such hydrogenation is known to the person skilled in the art, for example from US-A-6,683,136. In a typical process, hydrogen is used to treat the nitrile rubber in a solvent such as toluene or monochlorobenzene to be hydrogenated at a temperature ranging from 100 DEG C to 150 DEG C and at a pressure ranging from 50 to 150 bar for 2 to 10 hours do.

When heterogeneous catalysts are used in the preparation of hydrogenated carboxy nitrile rubbers by hydrogenation of the corresponding carboxy nitrile rubbers, supported catalysts based on palladium are generally used.

When the used hydrogenated nitrile rubber (a) or a plurality of hydrogenated nitrile rubbers (a) are used, the Mooney viscosity (ML 1 + 4, Measured at 100 DEG C) is in the range of 10 to 120, preferably in the range of 15 to 100. [ The Mooney viscosity is determined here according to ASTM standard D1646.

The hydrogenated nitrile rubber of the present invention has a residual double bond (RDB) content of 10% or less, preferably 7% or less, particularly preferably 1% or less.

The hydrogenated nitrile rubber which can be used in the vulcanizable composition of the present invention has a glass transition temperature of less than -15 占 폚, preferably less than -20 占 폚, particularly preferably less than -25 占 폚.

This type of hydrogenated nitrile rubber (a) is commercially obtainable to some extent, but is accessible in all cases by manufacturing processes that can be found in the literature by those skilled in the art. Examples of hydrogenated nitrile rubbers include fully and partially hydrogenated nitrile rubbers (Therban < ( ^R ) > series from LANXESS Deutschland GmbH with acrylonitrile content in the range of 20 to 50 wt% (Zetpol ^占 series from Nippon Zeon Corporation). Examples of the hydrogenated acrylonitrile-butadiene / acrylonitrile / acrylate polymer is a means to access doyichilrandeu embe under Terre half ^® LT series, for example, anti-Terminus ^® LT 2157 and hotel half ^® LT 2007. Examples of the nitrile rubber is hydrogenated carboxy screen is accessed doyichilrandeu to embe under Terre half ^® XT Series. Examples of the hydrogenated nitrile rubber has a low Mooney viscosity thus improving workability is Terre ^® anti-AT sequences, for example, anti-Terminus AT ^® 3404 product.

The hydrogenated nitrile rubber may comprise one or more other copolymerizable monomers in the form of carboxylic acid or carboxylic acid ester with one or more unsaturated nitrile and repeating units of one or more conjugated dienes. These are hydrogenated carboxy nitrile rubbers (also abbreviated as HXNBR).

Suitable copolymerizable carboxylic acids are mono- or dicarboxylic acids and their esters with 3 to 18 C atoms with unsaturation at the?,? Positions. Preferred?,? - unsaturated carboxylic acids are acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid and mixtures thereof.

Esters of an alpha, beta -unsaturated carboxylic acid having 3 to 18 C atoms preferably include alkyl esters and alkoxyalkyl esters of the above carboxylic acids. Preferred esters of an alpha, beta -unsaturated carboxylic acid having 3 to 18 C atoms are methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and octyl acrylate, and 1-8 repeating ethylene glycols (Meth) acrylate. Preferred alkoxyalkyl esters are methoxyethyl acrylate and ethoxyethyl acrylate and mixtures thereof.

Preferred esters are the?,? - ethylenically unsaturated dicarboxylic acid monoesters, for example

O alkyl esters, especially C ₄ -C ₁₈ -alkyl esters, preferably n-butyl esters, tert-butyl esters, n-pentyl esters or n-hexyl esters, particularly preferably mono-n-butyl maleate, n-butyl fumarate, mono-n-butyl citraconate, mono-n-butyl itaconate;

O alkoxyalkyl esters, especially C ₄ -C ₁₈ -alkoxyalkyl esters, preferably C ₄ -C ₁₂ -alkoxyalkyl esters,

O hydroxyalkyl esters, especially C ₄ -C ₁₈ -hydroxyalkyl esters, preferably C ₄ -C ₁₂ -hydroxyalkyl esters,

O cycloalkyl esters, especially C ₅ -C ₁₈ -cycloalkyl esters, preferably C ₆ -C ₁₂ -cycloalkyl, particularly preferably monocyclopentyl maleate, monocyclohexyl maleate, monocycloheptyl maleate, But are not limited to, monocyclopentyl fumarate, monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclohexyl fumarate, monocyclohexyl fumarate, monocyclohexyl fumarate, monocyclohexyl fumarate, monocyclopentyl itaconate, Carbonate and monocycloheptyl itaconate,

O alkylcycloalkyl esters, especially C ₆ -C ₁₂ -alkylcycloalkyl esters, preferably C ₇ -C ₁₀ -alkylcycloalkyl, particularly preferably monomethylcyclopentyl maleate and monoethylcyclohexyl maleate, monoethyl cyclohexyl maleate, Methylcyclopentyl fumarate and monoethyl cyclohexyl fumarate, monomethylcyclopentyl citraconate and monoethyl cyclohexyl citraconate; Monomethylcyclopentyl itaconate and monoethyl cyclohexyl itaconate;

O aryl esters, especially C ₆ -C ₁₄ -aryl monoesters, preferably monoaryl maleate, monoaryl fumarate, monoaryl citraconate or monoaryl itaconate, particularly preferably monophenyl maleate or monoaryl maleate Benzyl maleate, monophenyl fumarate or monobenzyl fumarate, monophenyl citraconate or monobenzyl citraconate, monophenyl itaconate or monobenzyl itaconate or mixtures thereof,

O Unsaturated polycarboxylic acid polyalkyl esters such as dimethyl maleate, dimethyl fumarate, dimethyl itaconate or diethyl itaconate; or

O Alpha, beta -ethylenically unsaturated carboxylic acid esters containing amino groups, such as dimethylaminomethyl acrylate or diethylaminoethyl acrylate

to be.

The proportion of conjugated dienes and alpha, beta -unsaturated nitriles in HXNBR polymers can vary widely. The proportion of the conjugated diene or the whole is usually in the range of 40 to 90% by weight, preferably in the range of 55 to 75% by weight, based on the whole polymer. The proportion of the [alpha], [beta] -unsaturated nitrile or the whole is generally 9.9 to 60% by weight, preferably 15 to 50% by weight, based on the whole polymer. The amount of the additional monomer present is 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total polymer. In each case, the proportion of all monomers is 100% by weight in total.

Thus, the hydrogenated carboxy nitrile rubber can be prepared by reacting one or more unsaturated nitriles with one or more conjugated dienes and also with hydrogenated carboxy, based on one or more teronomers comprising and / or containing a carboxylate group Phenonitrile rubber HXNBR, where more than 50% of the double bonds present in the original XNBR were saturated.

Examples of suitable HXNBRs include but are not limited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, isobutyl, sec-butyl and tert-butyl groups of butadiene and acrylonitrile and acrylic acid and / or methacrylic acid and / or fumaric acid and / or maleic acid and / or fumaric acid and / Ethyl, propyl, isopropyl, n-butyl, isobutyl, n-hexyl and / or 2-ethylhexyl hemi-esters of acrylic acid and / or methacrylic acid, Is a hydrogenated carboxy nitrile rubber based on XNBR made from ethylhexyl ester.

Hydrogenated carboxy nitrile rubbers are accessible in a variety of ways:

As an example, it is possible to graft HNBR to a compound containing a carboxyl group.

They can also be obtained by hydrogenation of carboxy nitrile rubber (XNBR) . This type of hydrogenated carboxy nitrile rubber is described, for example, in WO-A-01/77185 .

It is also possible that another elastomer (e) is present with the at least one hydrogenated nitrile rubber (a). The other elastomer (e) is present in a weight ratio of 1: 5 to 5: 1 to the hydrogenated nitrile rubber.

Component (b) - Non-reinforcing inorganic filler

The vulcanizable composition of the present invention comprises at least one non-reinforcing inorganic filler as component (b).

For the purposes of the present invention, the term " non-reinforced " means a filler having a specific surface area (N ₂ surface area) of less than 10 m ² / g. The value mentioned in the description of the specific surface area of the non-reinforcing inorganic filler is a BET value, that is, a value measured in accordance with DIN-ISO 9277.

Component (b) is more than 40% by weight based on the total amount of component (b) silicate (SiO _2), and 10% or more of aluminum oxide by weight a specific surface area including the _{(Al 2 O 3) (N} 2 surface area) is 10 m ² / g is less than the inorganic filler.

Component (b) preferably has a specific surface area (N ₂ surface area) of at least 40 wt% silicate (SiO ₂ ) and at least 10 wt% aluminum oxide (Al ₂ O ₃ ) based on the total amount of component 10 m ² / g is less than the calcined kaolin.

Examples of preferred component (b) is a (commercially available from Hoffmann Mineral (Hoffmann Mineral)) silpit (SILFIT) ^® Z 91. Silpet Z 91 is a naturally occurring hybrid crystal of amorphous and crypto-crystalline silica containing lamellar kaolinite exposed to heat treatment. Silpet Z 91 has a surface area (BET) of 8 m ² / g, contains 86 wt% SiO ₂ and 13 wt% Al ₂ O ₃ and has a pH of 6,5.

The component (b) more preferably comprises 40 to 70 wt.% SiO ₂ and 30 to 60 wt.% _{Al 2} O ₃ and has a pH of 6.0 to 7.0 ± 0.5 (BET) and a surface area of 8 to 9 m ² It is a calcined kaolin / g.

Component (b) it is especially preferably 50 to 60% by weight of SiO ₂ and 35 to 45% by weight including the A _l2 O _3, and a pH of 6.4 to 6.6 ± 0.5 (BET) specific surface area of 8.3 to 8.7 m ² It is a calcined kaolin / g.

Component (b) comprises a very particularly preferably from 50 to 60% by weight, preferably of 55% by weight SiO _2, and 35 to 45% by weight, preferably of 41% by weight A _l2 O ₃ and, pH is 6.5 ± 0.5 and a (BET) surface area of 8.5 m ² / g. An example of a very particularly preferred component (b) is calcined kaolin Polestar ^® 200R (commercially available from Imerys). Paul reseuta ^® 200R it is prepared by heating the pulverized kaolin at a temperature of more than 1000 ℃.

The amount of the component (b) present in the vulcanizable composition of the present invention is preferably 50 to 100 parts by weight, particularly preferably 60 to 90 parts by weight, based on 100 parts by weight of the hydrogenated nitrile rubber (a).

Component (c) - basic sodium silicate

The vulcanizable composition of the present invention comprises at least one basic sodium silicate (c) .

For the purposes of the present invention, the term "basic sodium silicate" means sodium containing silicates having a pH of greater than 7 measured in a 5 wt% aqueous solution according to DIN ISO 787/9.

Component (c) has a pH of more than 7, preferably a pH of more than 8, particularly preferably a pH of between 8 and 12, measured very particularly preferably in a 5% aqueous solution according to DIN ISO 787/9 is a basic sodium silicate with a pH greater than 10.5 to 12. Examples of the alkaline silicate has a pH of greater than 7, it is a sodium aluminum silicate to obtain a fire kasil A1 ^® trademark of the process.

Component (c) is preferably sodium aluminosilicate and sodium orthosilicate (Na ₄ SiO ₄ ), sodium metasilicate (Na ₂ SiO ₃ ), disodium disilicate (Na ₂ Si ₂ O ₅ ) Basic sodium silicates from the group consisting of sodium trisilicate (Na ₂ Si ₃ O ₇ ), particularly sodium aluminum silicate.

Component (c) is particularly preferably sodium aluminum silicate .

Especially preferred examples of component (c) is a sodium aluminum silicate with (commercially available from Huber (Huber)) brand fifth Rex ^® 23 having pH 10 and a specific surface area (BET) 80.

Component (c) very particularly preferably has a pH (5 wt% in water) of 11.3 ± 0.7 in water measured according to DIN ISO 787/9 and the content of volatile constituents measured according to DIN ISO 787/2 5.5 ± 1.5, and a (BET) surface area of 65 ± 15 measured according to ISO 9277. Examples of very particularly preferred component (c) is a sodium aluminum silicate with (commercially available from available is accessible) Brand Fire kasil ^® A1.

The amount of the component (c) present in the vulcanizable composition of the present invention is preferably 5 to 50 parts by weight, particularly preferably 10 to 30 parts by weight, based on 100 parts by weight of the hydrogenated nitrile rubber (a).

The weight ratio of component (b) to component (c) is from 20: 1 to 1: 1, preferably from 10: 1 to 2: 1, particularly preferably from 5: 1 to 3:

Component (d) - peroxide compound

One or more peroxide compounds are used as the crosslinking agent as component (d) .

The following peroxide compounds are suitable, for example, as the peroxide compound (d)

Bis (4-chlorobenzoyl) peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane butyl perbenzoate, 2,2-bis (tert-butylperoxy) butene, 4,4-di-tert-butylperoxynonylvalerate, dicumyl peroxide, 2,5- (Tert-butylperoxy) hexane, tert-butyl cumyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) benzene, di- , Tert-butyl hydroperoxide, hydrogen peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl (tert-butylperoxy) (Tert-butylperoxycarbonate), ethyl 3,3-di (tert-butylperoxy) butyrate, ethyl 3,3-di tert-amylperoxy) butyrate, n-butyl 4,4-di (tert-butylperoxy) valerate (Tert-butylperoxy) butane, 1,1-di (tert-butylperoxy) cyclohexane, 3,3,5-trimethylcyclohexane, Butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyisobutyrate, tert- Butyl peroxybenzoate, oxy-2-ethyl hexanoate, tert-butyl peroxy pivalate, tert-amyl peroxy pivalate, tert-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, Butyl peroxybenzoate, tert-butyl peroxyacetate, tert-amyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyisobutyrate butyl peroxy-2-ethyl hexanoate, cumyl peroxyneodecanoate, 3-hydroxy-1,1-dimethyl butyl peroxyneodecanoate, 2,5-dimethyl- D( tert-butylperoxy) hexyne (3-di-tert-amyl) peroxide, 2,5-dimethyl-2,5-di (tert- butylperoxy) hexane, , 2,5-dimethyl-2,5-di (hydroperoxy) hexane, diisopropylbenzene monohydroperoxide and potassium peroxodisulfate.

The at least one peroxide compound of the vulcanizable composition of the present invention is preferably selected from the group consisting of organic peroxides, especially dicumyl peroxide, tert-butyl cumyl peroxide, bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethylhexane-2,5-dihydroperoxide, dibenzoyl peroxide, bis (2,4-dichlorobenzoyl) Butyl perbenzoate, butyl 4,4-di (tert-butylperoxy) valerate and / or 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclo Hexane.

The amount of the component (d) present in the vulcanizable composition of the present invention is preferably 1 to 20 parts by weight, particularly preferably 2 to 10 parts by weight, based on 100 parts by weight of the hydrogenated nitrile rubber (a).

The vulcanizable composition may also comprise other rubber additives. Typical rubber additives include, by way of example and not limitation, polymers, filler activators, oils, especially processed or extender oils, plasticizers, processing aids, accelerators, lubricants, But are not limited to, polyfunctional crosslinking agents, antiozonants, antiozonants, antioxidants, mold release agents, scorch retarders, other stabilizers and antioxidants, fibers including dyes, organic and inorganic fibers, and also fiber pulps, , Dimer, trimer or oligomer.

Filler activators that can be used are, in particular, organosilanes such as vinyltrimethyloxysilane, vinyldimethoxymethylsilane, vinyltriethoxysilane, vinyltris (2-methoxy-ethoxy) silane, N-cyclohexyl- Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, isooctyltrimethoxysilane, iso-octyltrimethoxysilane, Hexadecyltrimethoxysilane, or (octadecyl) methyldimethoxysilane. Other filler actives are, for example, triethanolamine having a molecular weight of 74 to 10000 g / mol or an interface-active material such as ethylene glycol. The amount of the filler activator is usually 0.5 to 10 parts by weight based on 100 parts by weight of the hydrogenated nitrile rubber (a).

Aging inhibitors that may be used are those that remove the least number of free radicals, especially among peroxide radicals. These are especially oligomerized 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), styrinated diphenylamine (DDA), octylated diphenylamine (OCD) It is the zinc salt of mercaptobenzimidazole (ZMB2). Other compounds that may be used with this are the known phenolic aging inhibitors, such as sterically hindered phenols or phenylene diamine based aging inhibitors. Combinations of the indicated age inhibitors may also be used.

A conventionally used amount of the aging inhibitor is 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the hydrogenated nitrile rubber (a).

Examples of release agents that can be used include saturated or partially unsaturated fats and oleic acid or derivatives thereof (in the form of fatty acid esters, fatty acid salts, fatty alcohols or fatty acid amides), and also products which can be applied to the mold surface, For example, products based on low-molecular weight silicone compounds, products based on fluoropolymers and also products based on phenolic resins.

The amount of the release agent used as the mixture component is 0.2 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the hydrogenated nitrile rubber (a).

It may be desirable to use an antioxidant in the compositions of the present invention. Examples of the conventional antioxidant is of p- dequeue mildi phenylamine (Now guard (Naugard) ^® 445), bulka Knox (Vulkanox) ^® DDA (styrenated diphenylamine), bulka Knox ZMB2 ^® (methyl mercaptobenzimidazole zinc salt), bulka Knox ^® HS (polymerized 1,2-dihydro-2,2,4-trimethyl quinoline) and Irganox (Irganox) ^® 1035 (thiodiethylene bis (3,5-di -tert- butyl -4-hydroxy) hydrocinnamate or thiodiethylene bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate).

Another possibility is to is to enhance the vulcanizates with enhanced system made of a glass according to the teachings of US-A-4,826,721, and also reinforced with the aromatic polyamide (aramid (Aramid) ^®).

In a preferred embodiment, the vulcanizable composition of the present invention comprises

a) 100 parts by weight of at least one hydrogenated nitrile rubber ,

b) a specific surface area (N ₂ surface area) is less than 10 m ² / g comprising the component (b) on the basis of the total amount of at least 40% by weight of silicate (SiO _2), and 10% or more of aluminum oxide by weight (Al ₂ O ₃ a) of 50 to 100 parts by weight, preferably 60 to 90 parts by weight, of at least one inorganic filler ,

c) 5 to 50 parts by weight, preferably 10 to 30 parts by weight, of at least one basic sodium silicate ,

d) at least one peroxide compound , preferably selected from the group consisting of dicumyl peroxide, tert-butyl cumyl peroxide, bis- (tert-butyl-peroxy-isopropyl) 1 to 20 parts by weight, preferably 2 to 10 parts by weight, of dimethylhexane 2,5-dihydroperoxide, 2,5-dimethylhex-3-in 2,5-dihydroperoxide or dibenzoylperoxide,

e) 0 to 200 parts by weight, preferably 0 to 100 parts by weight of at least one conventional rubber additive

.

In a particularly preferred embodiment, the vulcanizable composition of the present invention comprises

(a) 100 parts by weight of at least one hydrogenated nitrile rubber ,

(b) 50 to 60 wt.%, preferably 55 wt.% SiO ₂ and 35 to 45 wt.%, preferably 41 wt.% Al ₂ O ₃ , based on the total amount of component (b) At least one calcined kaolin having a (BET) surface area of 8.5 m < ² > / g, measured according to ISO 787/9, in water (5 wt% part,

(c) the pH (5% by weight in water) in water measured according to DIN ISO 787/9 is 11.3 ± 0.7, the content of volatile constituents measured according to DIN ISO 787/2 is 5.5 ± 1.5, and ISO 9277 From 10 to 30 parts by weight of at least one sodium aluminum silicate having a (BET) surface area of 65 賊 15,

(d) at least one peroxide compound , preferably at least one peroxides selected from the group consisting of dicumyl peroxide, tert-butyl cumyl peroxide, bis (tert-butylperoxyisopropyl) benzene, 2 to 10 parts by weight of 2,5-dihydroperoxide, 2,5-dimethylhex-3-in 2,5-dihydroperoxide or dibenzoyl peroxide,

(e) 0 to 100 parts by weight of at least one conventional rubber additive

.

The present invention also provides a process for producing the above-mentioned vulcanizable composition of the present invention wherein all of components (a), (b), (c) and (d) are mixed. This can occur using devices and mixing devices known to those skilled in the art.

The order in which the components are mixed with one another is not fundamentally important, but is instead chosen to suit the mix assembly available in each case.

Here, mixing of components (a), (b), (c) and (d) can occur in a typical mixing system familiar with the rubber industry required by temperature. i) Mixing assemblies that operate batch-wise in the form of a mixing roll or an internal mixer, and ii) Mixing assemblies that operate continuously, such as a mixing extruder.

In a particularly proven method, the mixing of components (a), (b), (c) and (d) is carried out at a given mixer temperature in the range of about 30 ° C to 40 ° C, It is possible to apply a shear force sufficiently high to achieve good mixing with the mixing assembly described above.

Alternatively, mixing may be performed at a higher temperature with an appropriate assembly. In particular cases it may be necessary to start mixing the components (a), (b) and (c) and to avoid further mixing of the peroxide compound (d) until the end of the procedure. This additional mixing can take place, for example, in the mixing assembly of the end section of the nozzle just prior to ejecting the mixture onto the substrate / into the mold.

After mixing the components of the present invention, the vulcanizable composition may be prepared in a form known in the art as, for example, a " skin ", a feed strip or a feed slab, or else in the form of pellets or granules . They may be compressed or injection-molded in a mold and crosslinked under suitable conditions suitable for the peroxide compound used.

The present invention also provides a process for the production of vulcanizates, wherein the vulcanizable composition of the present invention of this type is subjected to vulcanization, that is to say the introduction of energy, in particular to heat treatment.

The energy may be introduced in the form of thermal or radiant energy, as required by the type of peroxide compound (d) selected in the vulcanizable composition.

The preparation of the vulcanization product by heat treatment is carried out such that the vulcanizable composition of the present invention is exposed to a suitable mold in a conventional manner, preferably at a temperature in the range of from 120 캜 to 200 캜, particularly preferably in the range of from 140 캜 to 180 캜.

During the crosslinking of the vulcanizable composition of the present invention, the peroxide compound (d) induces free-radical crosslinking with the hydrogenated nitrile rubber (a) used.

Further, the present invention provides a vulcanized product obtained by crosslinking, i.e., vulcanization, of the vulcanizable composition of the present invention .

The invention also provides the use of vulcanizates as gaskets, belts, roll coatings, hoses and cables.

Example:

Preparation, vulcanization and characterization of rubber compositions

The primary mixed assembly used was a mixed-roll system with a roll diameter of 200 mm, with a roll cooled to 30 占 폚 in Troester (WNU3). The hydrogenated nitrile rubber (a) was charged to the system and all other components were added in sequence (b), then (c), then (d) (see list of ingredients below). The rotational speed and friction ratio of the rolls were controlled to provide a stable skin. After a mixing time of about 5 minutes, the mixing was terminated and the product was discharged from the rolls in the form of a skin. The skins were vulcanized in a platen press at 180 DEG C for 15 minutes.

Ingredients used:

Thermal half ^® LT2007 acrylate-containing hydrogenated nitrile rubber, ACN content: 21 ± 1.5% by weight, Mooney viscosity ML 1 + 4 @ 100 ℃: 74 ± 10 MU, the residual double bond content: ≤0.9%. This hydrogenated nitrile rubber is commercially available from Lansdes Deutschland GmbH.

Thermal half ^® 3607 a hydrogenated nitrile rubber, ACN content: 36 ± 1.5% by weight, Mooney viscosity ML 1 + 4 @ 100 ℃: 66 ± 7 MU, residual double bond content: ≤0.9%. This hydrogenated nitrile rubber is commercially available from Lansdes Deutschland GmbH.

Paul reseuta ^® 200R 55% by weight including SiO _2, 41% by weight of Al ₂ O ₃ and, pH is 6.5 ± 0.5 a (BET) specific surface area of 8.5 m² / g is a calcined kaolin from the ephemeris.

Fire and kasil ^® A1 and DIN ISO a 11.3 ± 0.7 (5% by weight of water) pH of the measured object according to the 787/9 and the content of volatile constituents, measured according to DIN ISO 787/2 5.5 ± 1.5, ISO Sodium aluminum silicate from Lanses with a (BET) surface area of 65 +/- 15,

Peoka DOX ^® 14-40 Akzo Nobel Polymer Chemicals's bibeuyi (Akzo Nobel Polymer Chemicals BV) commercially available silica-supported 40% of di (tert- butylperoxyisopropyl) benzene from.

N990 Carbon black from Orion Engineered Carbon.

Uni-Flex (Uniplex) ^® 546 is accessed doyichilrandeu geem possible trioctyl tree commercially from beha trimellitate (TOTM).

Commercially available from Magnet light (Maglite) ^® MgO, CP Hall (Hall).

4,4'-bis- (1,1-dimethylbenzyl) -diphenylamine available from Luvomaxx ^® CDPA Lehmann and Voss.

Zinc salt of bulka Knox ^® ZMB2 / C5 is commercially available methyl 4 and 5 from the process doyichilrandeu geem beha-2-mercaptobenzothiazole.

Silquest (Silquest) ^® RC1 Momentive Performance Materials organic silane commercially available from (Momentive Performance Materials).

TAIC triallyl isocyanurate, 70% masterbatch, commercially available from Kettlitz Chemie GmbH & Co KG.

Active zinc oxide A commercially available zinc oxide from Lansdes Deutschland GmbH.

Commercially available trimethylolpropane trimethacrylate, 70% masterbatch from TRIM Ketlitz Chemie GmbH < RTI ID = 0.0 >

All " phr " amounts mentioned in the tables refer to parts per 100 parts of rubber. The total of all the elastomeric components comprising at least one hydrogenated nitrile rubber corresponds to 100 phr.

The crosslink density was determined using an oscillating frequency of 1.7 Hz and an angle of 0.5 [deg.] C for 30 minutes at 180 [deg.] C with a Moving Die Rheometer (MDR 2000E).

For the tensile test , the vulcanizable mixture was vulcanized at 180 占 폚 to prepare a 2 mm sheet. A dumbbell-shaped test sample was punched out of the sheet and the tensile strength and elongation were determined according to ASTM D2240-81.

The hardness was determined by a hardness meter according to ASTM D2240-81.

The compression set was determined according to DIN ISO 850 Part A.

The aging behavior of the vulcanizates was determined in accordance with DIN 53508.

EXAMPLES 1-4: All embodiments of the present invention are characterized in that there is * after each example number in Tables 1 to 4 below.

Table 1: Curable compositions

The compositions of the present invention 2 * and 3 * are the addition hydrogenated nitrile rubber (component (a)) and a peroxide compound (component (d)), more than 40% by weight of silicate (SiO ₂₎ and 10% by weight or more of aluminum oxide with (Component (b)) and also basic sodium silicate (component (c)) having a specific surface area (N ₂ surface area) of less than 10 m ² / g comprising aluminum oxide (Al ₂ O ₃ )

Table 2: Vulcanization test

Composition 2 * of the present invention comprising fully hydrogenated acrylate-containing nitrile rubber has a lower elongation at break than the composition comprising only carbon black as a reinforcing filler (see Comparative Example 5).

Composition 4 * of the present invention comprising fully hydrogenated nitrile rubber has a lower elongation at break than the composition comprising only carbon black as a reinforcing filler (see Comparative Example 6).

Table 3: Properties of vulcanized rubber composition

The rubber compositions 2 * and 4 * of the present invention have a low temperature compression set at 175 DEG C / 168 hours lower than comparative vulcanizates 1 and 3 without components (b) and (c). The rubber compositions 2 * and 4 * of the present invention all have a high temperature compression set of less than 45%.

The aging behavior was characterized by aging all vulcanizates according to DIN 53508 for 7 days (168 hours) at 175 ° C.

The values mentioned in Table 4 were then determined at a test temperature of 23 [deg.] C.

Table 4: Properties of vulcanized rubber compositions after aging at 175 ° C for 168 hours

A series of experiments show that the vulcanizates prepared according to the invention, i.e. the vulcanized rubber compositions 2 * and 4 *, exhibit considerably higher values for the high pressure compression set and for the aging characteristics after prolonged heat-air aging compared to the comparative vulcanizates 1 and 3 (Particularly regarding the elongation at break DELTA EB and hardness DELTA H).

Claims (15)

(a) at least one hydrogenated nitrile rubber,
(N ₂ surface area) comprising at least 40% by weight of silicate (SiO ₂ ) and at least 10% by weight of aluminum oxide (Al ₂ O ₃ ) based on the total amount of component (b) is 10 m ² / g ≪ / RTI > at least one inorganic filler,
(c) at least one basic sodium silicate and
(d) at least one peroxide compound
≪ / RTI > The vulcanizable composition according to claim 2, wherein the content of the residual double bond (RDB) in the component (a) is not more than 10%, preferably not more than 7%, particularly preferably not more than 1%. 3. A composition according to claim 1 or 2, wherein component (a) comprises one or more unsaturated nitrile and one or more other copolymerizable monomers in the form of a carboxylic acid or carboxylic acid ester together with repeating units of one or more conjugated dienes, But are not limited to, acrylic acid, methacrylic acid, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, PEG having 1 to 8 repeating ethylene glycol units Methacrylate, methoxyethyl acrylate or ethoxyethyl acrylate, or a mixture thereof. The vulcanizable composition according to any one of claims 1 to 3, wherein the amount of the component (b) to be used is 50 to 100 parts by weight, preferably 60 to 90 parts by weight based on 100 parts by weight of the hydrogenated nitrile rubber (a) . The first surface area comprises a process according to any one of the preceding, component (b) silicate (SiO _2), and 10% or more of aluminum oxide by weight (Al ₂ O ₃₎ of 40% or more by weight based on the total amount of the to claim 4, wherein (N ₂ surface area) of less than 10 m ² / g is used as component (b). The vulcanizable composition according to any one of claims 1 to 5, wherein the amount of the component (c) to be used is 5 to 50 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the hydrogenated nitrile rubber (a) . Claim 1 to according to any one of claim 6, wherein the alkaline sodium silicate, sodium orthosilicate (Na ₄ SiO _4), sodium metasilicate (Na ₂ SiO _3), di-sodium di-silicate (Na ₂ Si ₂ O ₅₎ , sodium trisilicate _{(Na 2 Si 3 O 7)} , and particularly preferably vulcanized is sodium aluminum silicate is used as component (c) composition. 8. A composition according to any one of claims 1 to 7, wherein the pH (5 wt.% In water) in water measured according to DIN ISO 787/9 is 11.3 0.7 and the volatile composition measured according to DIN ISO 787/2 Wherein the sodium aluminum silicate having a component content of 5.5 +/- 1.5 and a (BET) surface area of 65 +/- 15 measured according to ISO 9277 is used as component (c). 9. A composition according to any one of claims 1 to 8, wherein component (b) is used in an amount of from 20: 1 to 1: 1, preferably from 10: 1 to 2: 1, particularly preferably from 5: 1 to 3: 1. The vulcanizable composition according to any one of claims 1 to 9, wherein the amount of the component (d) to be used is 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the hydrogenated nitrile rubber (a) . 11. The process according to any one of claims 1 to 10, wherein the dicumyl peroxide, tert-butyl cumyl peroxide, bis (tert-butylperoxyisopropyl) benzene, Dimethylhexane 2,5-dihydroperoxide, 2,5-dimethylhex-3-in 2,5-dihydroperoxide, dibenzoylperoxide, bis (2,4-dichlorobenzoyl) peroxide, (Tert-butylperoxy) valerate or 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane is used as component (d) Vulcanizable composition. 12. The method according to any one of claims 1 to 11,
(a) 100 parts by weight of at least one hydrogenated nitrile rubber,
(N ₂ surface area) comprising at least 40% by weight of silicate (SiO ₂ ) and at least 10% by weight of aluminum oxide (Al ₂ O ₃ ) based on the total amount of component (b) is 10 m ² / g 50 to 100 parts by weight, preferably 60 to 90 parts by weight, of at least one inorganic filler,
(c) 5 to 50 parts by weight, preferably 10 to 30 parts by weight, of at least one basic sodium silicate with a pH in water (5% by weight in water) of more than 7, measured according to DIN ISO 787/9, and
(d) 1 to 20 parts by weight, preferably 2 to 10 parts by weight, of at least one peroxide compound
≪ / RTI > 13. The method according to any one of claims 1 to 12,
(a) 100 parts by weight of at least one hydrogenated nitrile rubber,
(b) water measured in accordance with DIN ISO 787/9, comprising 50 to 60 wt.%, preferably 55 wt.% SiO ₂ and 35 to 45 wt.%, preferably 41 wt.% Al ₂ O ₃ 50 to 100 parts by weight, preferably 60 to 90 parts by weight, of calcined kaolin having a (BET) surface area of 8.5 m ² / g, measured in accordance with ISO 9277, of 6.5%
(c) the pH (5% by weight in water) in water measured according to DIN ISO 787/9 is 11.3 ± 0.7, the content of volatile constituents measured according to DIN ISO 787/2 is 5.5 ± 1.5, and ISO 9277 5 to 50 parts by weight, preferably 10 to 30 parts by weight, of sodium aluminum silicate having a (BET) surface area of 65 占 15,
(d) at least one peroxide compound, preferably at least one peroxides selected from the group consisting of dicumyl peroxide, tert-butyl cumyl peroxide, bis (tert-butylperoxyisopropyl) benzene, 2,5-dihydroperoxide, 2,5-dimethylhex-3-in 2,5-dihydroperoxide or dibenzoyl peroxide in an amount of 1 to 20 parts by weight, preferably 2 to 10 parts by weight
≪ / RTI > A vulcanized product obtainable by vulcanization of the vulcanizable composition according to any one of claims 1 to 13. The use of the vulcanizate according to claim 14 as a gasket, belt, roll coating, hose and cable.